1-tridecen-6-yne | 186002-89-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1-tridecen-6-yne
• 英文别名: Tridec-1-en-6-yne
• CAS: 186002-89-1
• 化学式: C₁₃H₂₂
• 分子量: 178.318
• InChiKey: GRTIPBDFGMHWRS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-tridecen-6-yne 在 重水 、 n-Bu3MnMgBr 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 以92%的产率得到(1E)-1-(1-deuterioheptylidene)-2-(deuteriomethyl)cyclopentane
  参考文献：
  名称：

  Tributylmanganate(II)-Mediated Cyclization of Enynes

  摘要：

  用三丁基二价锰处理烯炔，得到了含有亚烷基取代基的环化产物。例如，1-十三烯-6-炔或1-十四烯-7-炔在用三丁基二价锰处理后，分别以67%或50%的产率生成1-亚庚基-2-甲基环戊烷或1-亚庚基-2-甲基环己烷。而三甲基乙烯基硅醚的3-癸炔-1-醇与三丁基二价锰反应，则以良好产率得到4-亚庚基-2,2,3-三甲基-1-氧-2-硅杂环己烷。

  DOI：

  10.1246/bcsj.73.1903
• 作为产物：
  描述：

  1-辛炔 、 5-溴-1-戊烯 在 caesium carbonate copper(l) iodide 、 [(ν³-allyl)PdCl]2 、 1,3-二(金刚烷-1-基)氯化咪唑 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以57%的产率得到1-tridecen-6-yne
  参考文献：
  名称：

  系链烯烃在镍催化添加到炔烃中的配体可切换导向效应

  摘要：

  描述了醛与包含系链烯烃的炔烃的镍催化还原偶联，其中区域选择性的程度和意义由系链的长度和添加剂的存在或不存在控制。当炔烃和烯烃被四个键分开时，观察到非常高（> 95:5）的区域选择性。使用单齿膦作为添加剂导致以相等和相反的选择性（5：> 95）形成相反的区域异构体。这些结果为在区域选择性决定步骤中远程烯烃和金属中心之间的相互作用提供了强有力的证据，并表明有和没有添加剂的反应通过根本不同的机制进行。

  DOI：

  10.1021/ja0446799

文献信息

• Titanocene- and zirconocene-mediated cyclization of allyl propargyl ethers. Stereoselective synthesis of 3-methylenetetrahydrofurans
  作者：Katsukiyo Miura、Masashi Funatsu、Hiroshi Saito、Hajime Ito、Akira Hosomi

  DOI：10.1016/s0040-4039(96)02128-4

  日期：1996.12

  Low-valent titanium and zirconium reagents in situ prepared from metallocene dichlorides (Cp2MCl2: M = Ti, Zr) and magnesium powder activated by 1,2-dibromoethane smoothly reacted with allyl propargyl ethers to afford 3-methylenetetrahydrofurans in good yields. It is noteworthy that the Cp2Zr- and Cp2Ti-mediated cyclizations proceed with inverse stereoselectivity.

  由茂金属二氯化物（Cp 2 MCl 2：M = Ti，Zr）和被1,2-二溴乙烷活化的镁粉原位制备的低价钛和锆试剂与烯丙基炔丙基醚平稳反应，以高收率得到3-亚甲基四氢呋喃。值得注意的是，Cp 2 Zr和Cp 2 Ti介导的环化反应的立体选择性反演。
• Tandem Insertion of Halocarbenoids and Lithium Acetylides into Zirconacycles: A Novel Rearrangement to Zirconium Alkenylidenates by β-Addition to an Alkynyl Zirconocene
  作者：Jozef Stec、Emma Thomas、Sally Dixon、Richard J. Whitby

  DOI：10.1002/chem.201002962

  日期：2011.4.18

  Tandem insertion of 1,1‐dihalo‐1‐lithio species (halocarbenoids) and lithium alkynides into zirconacyclopentenes and zirconcyclopentanes affords carbocyclic products in high yields via an unusual rearrangement that probably involves addition of an organolithium species to the β‐position of a zirconium–alkyne complex to give an alkenylidene–zirconate species. A wide variety of cyclopentanoid organic

  将1,1–二卤代1–硫代化合物（卤代类固醇）和炔属锂串联插入到氧化锆环戊烯和锆环戊烷中可以通过不寻常的重排提供高收率的碳环产物，该重排可能涉及将有机锂物种添加到锆的β位上。炔烃复合物，可得到烯基-锆酸酯。使用这种多组分偶联剂，可以高产率快速组装各种各样的环戊烷类有机结构。在某些情况下，主要的副反应是β-氢化物消除中间的环戊基或环戊烯基锆茂。
• Aldehyde Addition and Copper-Mediated Allylation of Bicyclic Alkoxytitanacyclopentenes and -Pentadienes:  New Selectivities and an Unusual Reaction
  作者：Hirokazu Urabe、Fumie Sato

  DOI：10.1021/ja982501e

  日期：1999.2.1

  Bicyclic titanacyclopentenes generated in situ from 1,6-enynes and (eta(2)-propene)Ti(O-i-Pr)(2) (1) reacted with aldehydes at their alkenyl-titanium bond in the absence or presence of Ti(O-i-Pr)(n)Cl(4-n) (n = 2 or 3) to give allyl alcohols such as 5-7 as a nearly single stereoisomer in good yields. Upon workup with DCl/D(2)O or iodine, deuterio and iodo derivatives, 8 and 9, were obtained. Bicyclic titanacyclopentadienes prepared analogously from 1,6- or 1,7-diynes and 1 also reacted with aldehydes in the presence of an additional equivalent of Ti(O-i-Pr)(2)Cl(2) to afford 1,2-dialkylidenecyclopentanes pr -cyclohexanes having an alcohol moiety in their side chain in good yields. In place of the simple hydrolysis, deuteriolysis or iodinolysis gave the corresponding derivatives such as 21 or 22. Treatment of 1,6-enyne 10 with 1 in the standard way and then with a slight excess of i-PrMgCl at -50 degrees C generated a new titanium species that, upon reaction with aldehydes, afforded unexpected adducts 34 and 41-45 virtually as a single isomer. Copper-mediated allylation of dialkoxytitanacyclopentene such as 3 with allyl bromide proceeded at their vinyl-titanium bond to give 48 and 50. Likewise, dialkoxytitanacyclopentadiene prepared from 29 and 1 underwent the regioselective copper-mediated mono-allylation to give a 9:1 mixture of 53 and 54. Upon workup with deuteriochloric acid, the corresponding deuterated product was obtained with a high degree of deuterium incorporation.
• Small Molecule Agonists of the Orphan Nuclear Receptors Steroidogenic Factor-1 (SF-1, NR5A1) and Liver Receptor Homologue-1 (LRH-1, NR5A2)
  作者：Richard J. Whitby、Jozef Stec、Raymond D. Blind、Sally Dixon、Lisa M. Leesnitzer、Lisa A. Orband-Miller、Shawn P. Williams、Timothy M. Willson、Robert Xu、William J. Zuercher、Fang Cai、Holly A. Ingraham

  DOI：10.1021/jm1014296

  日期：2011.4.14

  The crystal structure of LRH-1 ligand binding domain bound to our previously reported agonist 3-(E-oct-4-en-4-y1)-1-phenylamino-2-phenyl-cis-bicyclo[3.3.0]oct-2-ene 5 is described. Two new classes of agonists in which the bridgehead anilino group from our first series was replaced with an alkoxy or 1-ethenyl group were designed, synthesized, and tested for activity in a peptide recruitment assay. Both new classes gave very active compounds, particularly against SF-1. Structure-activity studies led to excellent dual-LRH-1/SF-1 agonists (e.g., RJW100) as well as compounds selective for LRH-1 (RJW101) and SF-1 (RJW102 and RJW103). The series based on 1-ethenyl substitution was acid stable, overcoming a significant drawback of our original bridgehead anilino-substituted series. Initial studies on the regulation of gene expression in human cell lines showed excellent, reproducible activity at endogenous target genes.
• Nickel-Catalyzed Carbocyanation of Alkynes with Allyl Cyanides
  作者：Yasuhiro Hirata、Tomoya Yukawa、Natsuko Kashihara、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1021/ja901374v

  日期：2009.8.12

  Allyl cyanides are found to add across alkynes in the presence of a nickel/P(4-CF3-C6H4)(3) catalyst to give polysubstituted 2,5-hexadienenitriles with defined stereo- and regiochemistry. Use of AlMe2Cl or AlMe3 as a Lewis acid cocatalyst accelerates the reaction and expands the substrate scope significantly. The cyano group in the allylcyanation products can be transformed to a hydroxymethyl or aminomethyl group to afford highly substituted allylic alcohols or amines. alpha-Siloxyallyl cyanides also add across alkynes selectively at the less hindered gamma-carbon to allow introduction of 3-oxo-propyl functionality after hydrolysis of the resulting silyl enol ethers. This particular carbocyanation reaction has been applied to the stereoselective construction of the trisubstituted double bond of plaunotol, an antibacterial natural product active against Helicobacter pylori.